JP2541656B2 - Naphthalocyanine compound and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a naphthalocyanine compound and a metal naphthalocyanine compound (hereinafter, both compounds are collectively referred to as “(metal) naphthalocyanine compound”), and their synthesis. 2, which has a phosphoryl group useful as an intermediate
Regarding a 3-di-substituted naphthalene compound and a method for producing them, more specifically, a novel naphthalocyanine compound that exhibits strong absorption for light in the near infrared region, is stable, and has good solubility in general organic solvents It is about.

(Prior Art) A naphthalocyanine compound is a compound that is stable to light, heat, temperature and the like and has excellent fastness, and is known as a near-infrared absorbing dye.

As near-infrared absorbing dyes, cyanine dyes, phthalocyanine dyes, dithionickel complexes, naphthoquinone dyes, anthraquinone dyes, indophenol dyes, azo dyes, etc. have been proposed, and their application fields are optical disks, compact disks, laser printers, Laser reading, electrophotographic photoreceptor, infrared cut filter for semiconductor light receiving element, etc.

In recent years, there have been many proposals for an optical recording medium for recording and reproducing voice, image, information and the like using a laser, especially a semiconductor laser. For example, as a proposal using a near-infrared absorbing dye in a recording layer of an optical disc, Sho 61-25886, JP 6
1-163891, JP-A-62-233287, JP-A-63-72594 (the above naphthalocyanine dyes), JP-A-62-122788,
Examples thereof include JP-A-63-39388 (above phthalocyanine dye), JP-A-60-252344, and JP-A 61-16891 (above cyanine dye).

By the way, converting a semiconductor laser into heat energy,
The dye used in the DRAW type, which forms pits, induces the difference in reflectance between the recorded part and the non-recorded part, and records the optical signal, has a large absorption in the laser emission range, and has a high reflectivity. It is required that the storage resistance be good and that a uniform recording medium film be obtained.

However, since the cyanine dye described above has low light fastness, an optical recording medium using the dye is not sufficiently satisfactory in storage stability. Further, among the proposals for phthalocyanine dyes and naphthalocyanine dyes, a uniform recording medium film cannot be obtained because few have excellent solubility and few have solubility in polar organic solvents. There was a problem in film formation depending on the coating method. Further, as a proposal of a naphthalocyanine compound for the purpose of improving solubility, for example, alkyl naphthalene ring disclosed in U.S. Pat.No. 4,492,750, JP 61-215662, JP 61-215663. Group, substituted silyl group, alkoxy group, phenoxy group or aralkoxy group-substituted naphthalocyanine compound, or JP-A-63-72
Examples thereof include naphthalocyanine compounds disclosed in JP-A-761 and JP-A-63-95269, in which the central metal is substituted with alkoxy or alkylsiloxy. However, these compounds have problems such as low solubility in organic solvents, such as alcohol, which hardly damage the guide grooves on the substrate such as polycarbonate.

(Problems to be Solved by the Invention) In view of the above circumstances, the present invention has excellent ability to absorb near-infrared light and can be advantageously used for film formation of an optical recording medium by a coating method such as spin coating. An object of the present invention is to provide a novel (metal) naphthalocyanine compound having excellent properties.

(Means for Solving the Problem) The present inventor has focused on a naphthalocyanine compound having excellent light resistance in order to solve the above-mentioned problems in the near-infrared absorbing dye, and the naphthalene ring forming the aryl group has an aryl group. , By substituting a phosphoryl group having an alkyl group or an alkoxy group, it is excellent not only in the absorption performance of the emission wavelength of a semiconductor laser but also in various organic solvents, particularly in a polar solvent such as an alcohol solvent. The present invention has been completed by finding that it is possible to obtain such a (metal) naphthalocyanine compound.

That is, the general formula: [Where X is (However, R ¹ and R ² are each independently a hydroxyl group,
An alkyl group, an aryl group or an alkoxy group having 1 to 10 carbon atoms is shown. ), M represents 2H, a metal, a metal oxide or a metal chloride. ] The naphthalocyanine compound and metal naphthalocyanine compound represented by these, and its manufacturing method are provided.

The (metal) naphthalocyanine compound according to the present invention is characterized in that the group represented by X is substituted on the naphthalene ring.

In the above formula [1], the substituents X on the naphthalene ring are each independently an aryl group represented by R ¹ and R ² , an alkyl group or a phosphoryl group having an alkoxy group having 1 to 10 carbon atoms, and for example, , -P (= O) (C 6 H 5) 2, -P (=
_{O) (OC 2 H 5)} 2, -P (= O) (C 10 H 21) 2, -P
(= O) (OH) ₂ . Further, the substituent X may be substituted at any of the 5-position, 6-position, 7-position and 8-position of the naphthalene ring.

In the above formula [1], M represents 2H (hydrogen) when it is a naphthalocyanine compound, and Cu, Zn, Ni, Co, Fe, Ge, S when it is a metal naphthalocyanine compound.
Metals such as n, Pb, Ti, Cr, Mn, Al and In, Ti = O, V =
O, Sn = O and other metal oxides, or SiCl ₂ , GeCl ₂ , Al
Represents metal chlorides such as Cl, SnCl ₂ and InCl.

Also, the following general formula: [In the formula, X has the same meaning as described above. ] 2,3-Dicyanonaphthalene having a substitution X represented by the following is a synthetic intermediate of the above naphthalocyanine compound according to the present invention.

The substituent X may be substituted at either the 5-position or the 6-position of the naphthalene ring.

The synthetic method of the intermediate represented by the above general formula [2] is, for example, the reaction of 3- or 4-bromo-o-xylene with phosphine oxide or phosphite in the presence of a catalyst,
General formula [In the formula, X has the same meaning as described above. ] X-substituted-o-xylene represented by the following formula is obtained, and then this is reacted with N-bromosuccinimide to give a compound of the general formula: [However, in the formula, X has the same meaning as described above. ] The compound of the formula: It can be produced by reacting with fumaronitrile represented by

Examples of the phosphine oxide used in the synthesis of the compound represented by the above formula [3] include chlorodiethylphosphine oxide and chlorodiphenylphosphine oxide. Examples of the phosphite include methyl phosphite, ethyl phosphite and decyl phosphite. Examples of the catalyst used at this time include anhydrous nickel chloride and the like. The amounts of phosphine oxide and phosphite used are 1.0 to 1.1 mol and 1.1 to 1.2 mol, respectively, relative to 1 mol of 3- or 4-bromo-o-xylene. The amount of catalyst used at this time is 0.05 to 0.2 mol.

Further, the amount of N-bromosuccinimide used in the synthesis of the compound represented by the above formula [4] is determined by the formula [3].
X-substituted-o-xylene represented by
~ 4.5 mol is required.

The amount of fumaronitrile represented by the above formula [5] is 1.0 per 1 mol of the compound represented by the formula [4].
~ 1.3 mol is required.

The (metal) naphthalocyanine compound represented by the above formula [1] of the present invention can be synthesized in the same manner as the naphthalocyanine compound and the metal compound thereof.

That is, the synthesis of the naphthalocyanine compound represented by the above formula [1] (wherein M represents 2H) is carried out by, for example, converting the intermediate represented by the above formula [2] into a proton-donating accelerator such as 1,8 -In the presence of diazabicyclo [5,4,0] unde-7-cene, the reaction is carried out in an alcohol solvent to obtain a metal-free naphthalocyanine compound.

Examples of the alcohol solvent include n-butanol, n-amyl alcohol, 2-methoxyethyl alcohol, 2-ethoxyethyl alcohol and the like.
The amount used of the proton-donating accelerator should be at least stoichiometric with respect to 1 mol of the intermediate represented by the above formula [2]. Alcohol solvent is 500-2000ml, preferably 1000ml
However, it is not particularly limited.

Of the above naphthalocyanine compounds, R ¹ R ²
= OH can also be obtained, for example, by hydrolyzing the tetrakis (dialkoxyphosphoryl) naphthalocyanine compound obtained by the above-mentioned synthetic method with phosphoric acid hydrochloric acid water or the like.

Further, the synthesis of the metal naphthalocyanine compound represented by the above formula [1] (wherein M represents a metal, a metal oxide or a metal chloride) can be carried out, for example, by synthesizing an intermediate represented by the above [2] and a metal or The metal chloride or metal oxide is melted or reacted in a high boiling point solvent to obtain a metal naphthalocyanine compound. Examples of the metal include
Cu, Zn, Ni, Co, Fe, Ge, Sn, Pb, Ti, Cr, Mn, Al, In
Etc. Examples of the metal chloride include CuC
_{l, Cu 2 Cl 2, SnCl} 2, InCl 3 · 4H 2 O, AlCl 3, TiCl 4, SiC
l ₄ , GeCl ₄ , FeCl ₃ , SnCl _{4 and the} like. Examples of the metal oxide include PbO ₂ and PbO. In addition, as the high boiling point solvent, for example, trichlorobenzene and the like are generally used, but quinoline, chloronaphthalene,
Bromonaphthalene or the like can be used.

The amount of these used is 1/4 to 2 mol, preferably 3/10 to 4/10 mol of the above metal, metal chloride or metal oxide, relative to 1 mol of the intermediate represented by the formula [2]. .
The high boiling point solvent that may be used can be used in an appropriate amount depending on the reaction scale.

In addition, as another method for synthesizing the above metal naphthalocyanine compound, a compound of [However, in the formula, X has the same meaning as described above. ] The X-substituted naphthalene-2,3-carboxylic acid anhydride represented by the formula (1) is combined with the above metal or metal chloride or metal oxide in the presence of urea, and if desired, ammonium molybdate, ammonium vanadate, and arsenous acid. Alternatively, a catalyst such as ammonium phosphate is added, and a metal naphthalocyanine compound is obtained by melting or reacting in the above high boiling point solvent.

The reaction reagent is used in an amount of 5 to 10 mol of urea, 1/4 mol or more of the metal or metal chloride or metal oxide, and preferably 3 / mole to 1 mol of the compound represented by the formula [6]. 10 mol, preferably a high boiling solvent that may be used
It is 1000-1500 ml.

Furthermore, as another method for synthesizing the above metal naphthalocyanine compound, the following formula: [However, in the formula, X has the same meaning as described above. ] The X-substituted 1,3-diiminobenz (f) isoindoline represented by the formula (I) and the above metal or metal chloride or oxide are melted or reacted in the presence of a tertiary amine in the above high boiling point solvent to produce a metal naphthalocyanine compound. To get

Examples of the tertiary amine include triethylamine,
Tri-n-butylamine etc. are mentioned.

The amount of the above corner reaction reagent used is 1/4 to 2 mol, preferably 3/10 to 4 /, of the above metal or metal chloride or metal oxide per 1 mol of the compound represented by the formula [7]. Ten
Mol, a catalytic amount of the tertiary amine, and 100 to 2000 ml, preferably 500 to 1000 ml of the high boiling point solvent which may be used.

The naphthalocyanine compound of the present invention obtained as described above is good for various organic solvents (for example, alcohols, ketones, ethers, esters, aliphatic halogenated hydrocarbons, aromatics). In addition to exhibiting solubility
It has the property that the absorption characteristics of the electron spectrum change depending on the solvent. As a specific example, for example, the electronic spectrum of tetrakis (diphenylphosphoryl) metal-free naphthalocyanine shown in Example 3 described later has an absorption characteristic shown in FIG. 8 in a chloroform solvent, but tetrahydrofuran (hereinafter referred to as THF) is used. When a solvent is used, its absorption changes to the low wavenumber side, as shown in Figure-18.

(Effect of the invention) The novel naphthalocyanine compound according to the present invention is a green, blue, or brown compound which is excellent in absorption of near-infrared light having a transmission wavelength of 780 to 830 nm of a semiconductor laser typified by AlGaAs laser which is currently widely used. Alternatively, it is a black crystal or powder and is robust against light, heat, temperature, acid, and alkali. Moreover, it has excellent solubility in various organic solvents, particularly polar organic solvents, and compatibility with resins, and is useful as a near-infrared light absorbing dye.

Furthermore, since the novel naphthalocyanine compound according to the present invention has excellent solubility in polar organic solvents as described above, poly (meth) acrylate may be used during thin film formation by a coating method such as spraying, roller coating, dipping and spinning. A uniform and high-density recording layer can be obtained without melting the surface of the base of an optical recording medium using an organic resin such as a resin and a polycarbonate.

(Examples) Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

Example 1 4-diphenylphosphoryl-o-xylene Synthesis of Tetrahydrofuran (hereinafter referred to as dry THF) 100 which was previously distilled and dried using lithium aluminum hydride
Turning magnesium 2.83 g (0.1209 mol) was added to ml, and 4-bromo-o-xylene 19.6 g (0.1
A solution of 06 mol) in dry THF was added dropwise over a period of about 1 hour. After the dropping, the mixed solution is heated under reflux for about 1 hour,
After cooling to 5 to 10 ° C, a dry THF solution of 25 g (0.106 mol) of chlorodiphenylphosphine oxide was added dropwise over about 30 minutes while keeping this temperature range. After dropping, 5
After stirring at 0 to 60 ° C for 2 hours, the mixture was allowed to cool. After cooling, 100 ml of dilute hydrochloric acid water and 100 ml of diethyl ether were added, and the mixture was stirred for 30 minutes, and then extracted with 200 ml of diethyl ether three times. This solution was washed 3 times with a 5% sodium hydrogen carbonate solution, and then anhydrous sodium sulfate was added and dried. After concentrating the ether solution, 25 g of a white solid was obtained by column chromatography.

NMR spectrum value: CDCl ₃ solvent (see FIG. 1) δ value 7.45 (13H, br) 2.23 (6H, br-s) Example 2 3-diethoxyphosphoryl-o-xylene Synthesis of 3-bromo-o-xylene 25.0 g (0.135 mol) and anhydrous nickel chloride 2.0 g (0.015 mol) mixed solution in advance to 150-1
The mixture was heated at 60 ° C., and 26.9 g (0.162 mol) of triethylphosphite was added to this solution over 1 to 2 hours. After the completion of dropping, the mixture was stirred at this temperature for 4 hours. After cooling, 30 ml of water was added, the mixture was stirred for 30 minutes, and then extracted with 100 ml of diethyl ether three times. This solution was washed 3 times with a 5% sodium hydrogen carbonate solution, and then anhydrous sodium sulfate was added and dried.
After concentrating the ether solution, column chromatography gave 20.0 g of a colorless liquid.

NMR spectrum value: CDCl ₃ solvent (see FIG. 2) δ value 7.92-7.13 (3H, m) 4.13 (4H, dq, J _HH = J _Hp = 7.26 Hz) 2.50 (3H, s) 2.30 (3H, m) s) 1.33 (6H, t, J HH = 7.26Hz) example 3 4-diethoxyphosphoryl -o- xylene 20.8 g of a colorless liquid was obtained in the same manner as in Example 2, except that 3-bromo-o-xylene used in Example 2 was replaced with 4-bromo-o-xylene.

NMR spectrum value: CDCl ₃ solvent (see FIG. 3) δ value 7.66-7.28 (3H, m) 4.11 (4H, dq, J _HH = J _Hp = 7.04Hz) 2.30 (6H, s) 1.32 (6H, m) t, J _HH = 7.04 Hz) Example 4 6-diphenylphosphoryl-2,3-dicyanonaphthalene Synthesis of 4-diphenylphosphoryl-o-xylene 10.3 g (0.0
35mol) and 25.3g (0.142m) of N-bromosuccinimide
benzoic acid peroxide (0.3 g) was added to 100 ml of carbon tetrachloride solution and refluxed for 10 to 12 hours with a mercury lamp. After allowing to cool, the precipitated white solid was removed by suction filtration, and the carbon tetrachloride solution of the mother liquor was concentrated under reduced pressure. The obtained solid was washed with a very small amount of methanol and then dried under reduced pressure to obtain 21.3 g of 1,2- (bis (dibromomethyl) -4-diphenylphosphorylbenzene.

The analysis results of 1,2-bis (dibromomethyl) -4-diphenylphosphorylbenzene are as follows: 1) Elemental analysis value Calculated value (%): C; 38.61, H; 2.41 Measured value (%): C; 37.97, H; 2.39 2) NMR spectrum value: CDCl ₃ solvent δ value was 8.28-7.39 (13H, m) 7.26 (1H, s) 7.06 (1H, s).

Then, the obtained 1,2-bis (dibromomethyl) -4-
To a solution of diphenylphosphorylbenzene 21.3 g (0.034 mol) and fumaronitrile 3.5 g (0.045 mol) in anhydrous N, N-dimethylformamide 100 ml was added sodium iodide 23.2 g (0.155 mol) while stirring well, and under nitrogen atmosphere, 75
Stirred at 5 ° C for 5 hours. After the reaction, the mixture was poured into about 500 ml of ice water and stirred for several dozen minutes, and then sodium hydrogen sulfite was gradually added until the reddish brown aqueous solution became pale yellow, and then stirred for about 1 hour. The precipitated pale yellow solid was suction filtered, washed thoroughly with water, and dried under reduced pressure to obtain 8.5 g of a crude product.

By recrystallizing 7.0 g of this product from ethanol, 5.85 g of white crystals were obtained. It was confirmed from the following analysis results that this crystal was 6-diphenylphosphoryl-2,3-dicyanonaphthalene.

1) Elemental analysis value Calculated value (%): C; 76.19; H; 3.97; N; 7.41 Actual value (%): C; 75.53; H; 4.11; N; 7.45 2) NMR spectrum value: CDCl ₃ solvent… ( (See Fig. 4.) δ value 8.46-7.41 (15H, m) 3) IR spectrum (CHCl ₃ solution thin film method) (See Fig. 5) Attribution to nitrile C≡N stretching vibration at 2200 cm ^-1 Absorption 1210 cm ^-1 , 1175 cm ^-1 has absorption due to Ph ₂ P = O stretching vibration.

Example 5 6-Diethoxyphosphoryl-2,3-dicyanonaphthalene Synthesis of 4-diethoxyphosphoryl-o-xylene 47.7 g (0.1
97mol) and N-bromosuccinimide 144g (0.809mo)
Benzoyl peroxide (1.0 g) was added to carbon tetrachloride (500 ml) solution of (l), and the mixture was irradiated with light from a mercury lamp for 10 to 12 hours while refluxing.
After allowing to cool, the precipitated white solid was removed by suction filtration, and the carbon tetrachloride solution of the mother liquor was concentrated under reduced pressure.

A very small amount of ether was added to the obtained viscous liquid and ultrasonic waves were applied to precipitate a solid, which was filtered to obtain about 40 g of white crystals. This crystal is 1,2 from the analysis results below.
It was confirmed to be -bis (dibromomethyl) -4-diethoxyphosphorylbenzene.

1) Elemental analysis value Calculated value (%): C; 27.82, H; 2.90 Actual value (%): C; 26.25, H; 2.68 2) NMR spectrum value: CDCl ₃ solvent δ value 8.12-7.76 (3H, m) 7.23 (1H, s) 7.07 (1H, s) 4.17 (4H, dq, J _HH = J _Hp = 7.26Hz) 1.36 (6H, t, J _HH = 7.26Hz) Next, the obtained 1,2-bis (Dibromomethyl) -4-
23.2 g (0.155 mol) of sodium iodide was added to a solution of 20 g (0.036 mol) of diethoxyphosphorylbenzene and 3.5 g (0.045 mol) of fumaronitrile in 100 ml of anhydrous N, N-dimethylformamide while stirring well, and under a nitrogen atmosphere, 75 ° C
And stirred for 5 hours. After the reaction, the mixture was slowly added dropwise to 2000 ml of 5% hydrogen sulfite solution, and a white slurry rapidly formed. After completion of the dropping, salting out with sodium chloride was performed, suction filtration was performed, the obtained solid was sufficiently washed with water, and then dried under reduced pressure to obtain 5.1 g of a white solid. It was confirmed that this product was 6-diethoxyphosphoryl-2,3-dicyanonaphthalene based on the analysis results described below without further purification.

1) Elemental analysis value Calculated value (%): C; 61.15, H; 4.78, N; 8.92 Measured value (%): C; 60.09, H; 4.76, N; 8.89 2) NMR spectrum value: CDCl ₃ solvent… ( See Fig. 6.) δ value 8.61 (1H, s) 8.45 (1H, s) 8.41 (1H, s) 8.12 (1H, s) 8.04 (1H, s) 4.19 (4H, dq, J _HH ＝ J _Hp ＝ 7.04Hz) 1.36 (6H, t, J HH = 7.04Hz) 3) IR spectrum (CHCl ₃ solvent) (see Figure 7.) attributed to 2250 cm ^-1 nitrile C≡N stretching vibration absorbing 1290Cm ^-1 At 1260 cm ^−1, it has an absorption attributed to (C ₂ H ₅ O) ₂ P═O stretching vibration.

Example 6 Synthesis of tetrakis (diphenylphosphoryl) metal-free naphthalocyanine A mixture of 6-diphenylphosphoryl-2,3-dicyanonaphthalene (1,124 g, 3 mmol) and dry amyl alcohol (3 ml) was heated to reflux under a nitrogen atmosphere. About 0.50 ml (3.3 mmol) of 8,8-diazabicyclo [5,4,0] unde-7-sen
It dripped over 15 minutes. Then, the mixture was stirred under heating under reflux for about 10 hours, then allowed to cool to about 70 ° C., 30 ml of methanol was added, and the mixture was further stirred at this temperature for 1 hour. The deposited dark green solid was collected by filtration and washed with methanol. Next, this was again dispersed in 300 ml of methanol, heated under reflux for about 1 hour, suction filtered while hot, and thoroughly washed with methanol until the filtrate became transparent. The dark green solid collected by filtration was dried under reduced pressure to obtain 600 mg of a solid.

This was confirmed to be tetrakis (diphenylphosphoryl) metal-free naphthalocyanine from the following analysis results.

1) Elemental analysis value Calculated value (%): C; 76.09, H; 4.10, N; 7.40 Measured value (%): C; 72.80, H; 4.33; N; 7.23 2) Electronic spectrum (CHCl ₃ solution)… ( (See FIG. 8) Electronic spectrum (THF solution) (See FIG. 18) 3) IR spectrum (KBr method) (See FIG. 9) Example 7 Tetrakis (diethoxyphosphoryl) metal-free naphthalocyanine Synthesis 6- (diethoxyphosphoryl) -2,3-dicyanonaphthalene 1.2 g (4.7 mmol) and dry amyl alcohol 3 ml and 1,8-diazabicyclo [5,4,0] unde-7-cene 0.8 m
l (5.3 mmol) was reacted in the same manner as in Example 6, and after the reaction was completed, methanol and water were added in 5 ml portions, and the mixture was stirred,
Salting out was performed using sodium chloride. The obtained solid was collected by filtration, washed with water, and then washed with a solution of methanol / water = 3/7 until the filtrate became transparent. The dark green solid was dried under reduced pressure to obtain about 450 mg of solid.

1) Elemental analysis value Calculated value (%): C, 61.05; H, 4.93; N, 8.90 Measured value (%): C, 60.92; H, 4.90; N, 8.87 2) Electronic spectrum (CHCl ₃ solution)… ( (See FIG. 10) 3) IR spectrum (KBr method) (See FIG. 11) Example 8 Synthesis of tetrakis (dihydroxyphosphoryl) metal-free naphthalocyanine Tetrakis (diethoxyphosphoryl) metal-free synthesized in Example 7 A mixed liquid of 100 mg of naphthalocyanine and 100 ml of 10% hydrochloric acid was heated under reflux for about 5 hours, then allowed to cool, and a deep green solid was collected by filtration. After washing this with an appropriate amount of ion-exchanged water,
Wash with about 50 ml of methanol, dry under reduced pressure,
Obtained mg of solid.

This was confirmed to be tetrakis (dihydroxyphosphoryl) metal-free naphthalocyanine from the following analysis results.

1) Elemental analysis value Calculated value (%): C, 55.71; H, 2.90; N, 10.83 Measured value (%): C, 55.50; H, 2.87; N, 10.75 2) Electronic spectrum (5% sodium hydrogen carbonate aqueous solution) )
(See FIG. 12) 3) IR spectrum (KBr method) (See FIG. 13) Example 9 Synthesis of tetrakis (diphenylphosphoryl) vanadyl naphthalocyanine 6-diphenylphosphoryl-2,3-dicyanonaphthalene 1.0 g (2.65mmol), vanadium chloride 0.3g (1.33mmo
l), 0.5 ml of tri-n-butylamine and 3 ml of α-bromonaphthalene were heated and stirred at 180 to 200 ° C for about 3 hours, then allowed to cool to about 60 ° C, 50 ml of methanol was added, and After stirring at temperature for 1 hour, the precipitated dark green solid was collected by filtration. The filtrate was washed with methanol until it became colorless, dispersed in 300 ml of 3% hydrochloric acid water, and stirred at 70 to 80 ° C for about 1 hour. After being filtered, washed thoroughly with water,
Furthermore, it was washed with 300 ml of methanol, dried under reduced pressure, and
Obtained mg of solid.

This was confirmed to be tetrakis (diphenylphosphoryl) vanadyl naphthalocyanine from the following analysis results.

1) Elemental analysis value Calculated value (%): C, 73.00; H, 3.80; N, 7.09 Measured value (%): C, 70.13; H, 4.02; N, 6.84 2) Electronic spectrum (CHCl ₃ solution)… ( (See FIG. 14) 3) IR spectrum (KBr method) (See FIG. 15) Example 10 Synthesis of tetrakis (diphenylphosphoryl) chloroindium naphthalocyanine 6-diphenylphosphoryl-2,3-dicyanonaphthalene 1.5 g ( 4 mmol), indium chloride tetrahydrate 0.75 g (2.
(56 mmol) and quinoline 3 ml, and the mixture is heated and stirred at about 200 ° C for about 6 hours, then allowed to cool to about 60 ° C and methanol 60 ml.
Was added, and the mixture was further stirred at this temperature for 1 hour, and then the precipitated dark green solid was collected by filtration. Next, wash the filtrate with methanol until the filtrate is no longer colored, and then use 3% hydrochloric acid water 30
It was dispersed in 0 ml and stirred at 70 to 80 ° C. for about 1 hour. After filtration
After thoroughly washing with water, wash again with 300 ml of methanol,
After drying under reduced pressure, 500 mg of solid was obtained.

This was confirmed to be tetrakis (diphenylphosphoryl) chloroindium naphthalocyanine from the following analysis results.

1) Elemental analysis value Calculated value (%): C, 69.30; H, 3.61; N, 6.74 Measured value (%): C, 67.64; H, 3.82; N, 6.41 2) Electronic spectrum (CHCl ₃ solution)… ( (See Fig. 16.) 3) IR spectrum (KBr method) ... (See Fig. 17)

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an NMR spectrum diagram of the compound of Example 1, FIG.
The figure shows the NMR spectrum of the compound of Example 2, FIG. 3 shows the NMR spectrum of the compound of Example 3, and FIG.
5 is an NMR spectrum of the compound of Example 4, FIG. 5 is an IR spectrum of the compound of Example 4, FIG. 6 is an NMR spectrum of the compound of Example 5, and FIG. 7 is a compound of Example 5. IR spectrum of the compound of Example 6, FIG. 8 is an electronic spectrum of the compound of Example 6, FIG. 9 is an IR spectrum of the compound of Example 6, and FIG. 10 is an electronic spectrum of the compound of Example 7. FIG. 11 is an IR spectrum diagram of the compound of Example 7,
FIG. 12 is an electron spectrum diagram of the compound of Example 8, FIG.
The figure shows the IR spectrum of the compound of Example 8, and FIG. 14 shows
15 is an electron spectrum diagram of the compound of Example 9, FIG. 15 is an IR spectrum diagram of the compound of Example 9, FIG. 16 is an electron spectrum diagram of the compound of Example 10, and FIG. 17 is a compound of Example 10. FIG. 18 shows the IR spectrum of the compound of Example 6, and FIG.

Claims (7)

(57) [Claims] 1. A general formula: [Where X is (However, R ¹ and R ² are each independently a hydroxyl group,
An alkyl group, an aryl group or an alkoxy group having 1 to 10 carbon atoms is shown. ), M represents 2H, a metal, a metal oxide or a metal chloride. ] The naphthalocyanine compound and metal naphthalocyanine compound represented by these. 2. A general formula: [In the formula, X has the same meaning as described above. ] The intermediate of the compound of Claim 1 represented by these. 3. A compound represented by the general formula by reacting 3- or 4-bromo-o-xylene with phosphine oxide or phosphite. [In the formula, X has the same meaning as described above. ] X-substituted-o-xylene represented by the following formula is obtained, and then this is reacted with N-bromosuccinimide to give a compound of the general formula: [In the formula, X has the same meaning as described above. ] The compound of the formula: The method for producing an intermediate represented by the general formula [2] according to claim 2, wherein the intermediate is represented by the formula (2). 4. The general formula [1] characterized in that the intermediate according to claim 2 is reacted in an alcohol solvent in the presence of a proton-donating type accelerator (wherein M represents 2H). )
A method for producing a naphthalocyanine compound represented by: 5. The general formula [1] in which the intermediate according to claim 2 is reacted with a metal or a metal chloride or oxide in a melting or high boiling point solvent (wherein M is a metal, a metal oxide or A method for producing a metal naphthalocyanine compound represented by the formula (1). 6. A general formula: [However, in the formula, X has the same meaning as described above. ] The X-substituted naphthalene-2,3-dicarboxylic acid anhydride represented by the formula and a metal or metal chloride or oxide are reacted in the presence of urea in a molten or high-boiling solvent [1] (provided that M Represents a metal, a metal oxide or a metal chloride.) The method for producing a metal naphthalocyanine compound represented by. 7. A general formula: [However, in the formula, X has the same meaning as described above. ] The X-substituted 1,3-diiminobenz (f) isoindoline represented by the formula and a metal or metal chloride or oxide are reacted in the presence of a high boiling point solvent in the presence of a molten or tertiary amine [1] (provided that , M represents a metal, a metal oxide or a metal chloride.).